TY - JOUR
T1 - Catalytic hydrogen atom transfer from hydrosilanes to vinylarenes for hydrosilylation and polymerization
AU - Asgari, Parham
AU - Hua, Yuanda
AU - Bokka, Apparao
AU - Thiamsiri, Chanachon
AU - Prasitwatcharakorn, Watcharapon
AU - Karedath, Ashif
AU - Chen, Xin
AU - Sardar, Sinjinee
AU - Yum, Kyungsuk
AU - Leem, Gyu
AU - Pierce, Brad S.
AU - Nam, Kwangho
AU - Gao, Jiali
AU - Jeon, Junha
N1 - Publisher Copyright:
© 2019, The Author(s), under exclusive licence to Springer Nature Limited.
PY - 2019/2/1
Y1 - 2019/2/1
N2 - Because of the importance of hydrogen atom transfer (HAT) in biology and chemistry, there is increased interest in new strategies to perform HAT in a sustainable manner. Here, we describe a sustainable, net redox-neutral HAT process involving hydrosilanes and alkali metal Lewis base catalysts—eliminating the use of transition metal catalysts—and report an associated mechanism concerning Lewis base-catalysed, complexation-induced HAT. The catalytic Lewis base-catalysed, complexation-induced HAT is capable of accessing both branch-specific hydrosilylation and polymerization of vinylarenes in a highly selective fashion, depending on the Lewis base catalyst used. In this process, the Earth-abundant, alkali metal Lewis base catalyst plays a dual role. It first serves as a HAT initiator and subsequently functions as a silyl radical stabilizing group, which is critical to highly selective cross-radical coupling. An electron paramagnetic resonance study identified a potassiated paramagnetic species, and multistate density functional theory revealed a high HAT character, yet multiconfigurational nature in the transition state of the reaction.
AB - Because of the importance of hydrogen atom transfer (HAT) in biology and chemistry, there is increased interest in new strategies to perform HAT in a sustainable manner. Here, we describe a sustainable, net redox-neutral HAT process involving hydrosilanes and alkali metal Lewis base catalysts—eliminating the use of transition metal catalysts—and report an associated mechanism concerning Lewis base-catalysed, complexation-induced HAT. The catalytic Lewis base-catalysed, complexation-induced HAT is capable of accessing both branch-specific hydrosilylation and polymerization of vinylarenes in a highly selective fashion, depending on the Lewis base catalyst used. In this process, the Earth-abundant, alkali metal Lewis base catalyst plays a dual role. It first serves as a HAT initiator and subsequently functions as a silyl radical stabilizing group, which is critical to highly selective cross-radical coupling. An electron paramagnetic resonance study identified a potassiated paramagnetic species, and multistate density functional theory revealed a high HAT character, yet multiconfigurational nature in the transition state of the reaction.
UR - http://www.scopus.com/inward/record.url?scp=85060796651&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85060796651&partnerID=8YFLogxK
U2 - 10.1038/s41929-018-0217-z
DO - 10.1038/s41929-018-0217-z
M3 - Article
C2 - 31460492
AN - SCOPUS:85060796651
SN - 2520-1158
VL - 2
SP - 164
EP - 173
JO - Nature Catalysis
JF - Nature Catalysis
IS - 2
ER -